JPH06199624A - Dental adhesive set - Google Patents

Abstract

PURPOSE:To provide a dental adhesive set capable of simultaneously pretreating the enamel and dentine of teeth and of strongly adhering to both the parts. CONSTITUTION:The dental adhesive set comprises a preliminarily treating agent consisting mainly of an organic acid or its salt and water and having a pH of 0.8-2.2 and an adhesive composition containing 100 pts.wt. of a vinylic monomer containing >=39wt.% of an acidic group-containing vinylic monomer of formula I (R1 is H, methyl; R2 is 1-20C organic residue; m is 2-4; n is 1, 2) and 0.1-3 pts.wt. of a polymerization initiator (especially the combination of a photosensitizer and a photopolymerization initiator is preferable from the view-point of adhesive strength). The vinylic monomer of formula I used herein is e.g. a compound of formula II. The organic carboxylic acid is preferably citraconic acid, lactic acid, 1,3,5-pentane tricarboxylic acid, tricarballylic acid, acrylic acid, or the like, especially because of exhibiting strong adhesive strength to dentines.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the field of dentistry,
The present invention relates to a dental adhesive set having a high adhesive strength with a tooth substance when filling and repairing a tooth.

[0002]

2. Description of the Related Art A composite restorative material called a composite resin is mainly used for the restoration of teeth damaged by caries or the like. This composite resin is generally used by filling the cavity of the tooth and then polymerizing and hardening. But,
Since this material itself does not have adhesiveness to the tooth structure, a dental adhesive is used together. This adhesive material is required to have an adhesive strength sufficient to overcome internal stress generated during curing of the composite resin, that is, tensile stress generated at the interface between the composite resin and the tooth structure. Otherwise, it may fall off due to long-term use in a harsh oral environment, and there may be a gap at the interface between the composite resin and the dentin, from which bacteria may invade and adversely affect the pulp. This is because.

Tooth is mainly composed of enamel and dentin. Since both have different structures and compositions, separate bonding operations have been conventionally required. That is, the enamel has been mechanically maintained by treating the enamel with an acid aqueous solution pretreatment material and etching the surface. On the other hand, in the case of dentin, mechanical maintenance is not always effective, so various acrylic adhesive components were added to the dental adhesive composition, and the surface was exclusively for dentin of a composition different from that of enamel. By a method of pretreating with a pretreatment material and further applying an undercoating agent called a primer, an adhesion operation which takes not only mechanical maintenance but also chemical affinity has been generally performed. However, such an operation method has many steps and is inferior in operability and requires time, and the adhesive force is not sufficient.

To explain the above facts in more detail, an aqueous phosphoric acid solution has been generally used as a pretreatment material for enamel. However, when the dentin is pretreated with phosphoric acid, not only is sufficient adhesive strength not obtained, but the phosphoric acid aqueous solution penetrates from the surface of the cavity of the dentin through the dentinal tubules into the tooth, and The problem of inspiration often occurred. Therefore, a method of using an organic carboxylic acid such as citric acid having a lower acid strength as a pretreatment material for dentin, which is changed to phosphoric acid, has been performed (Dental Science and Engineering Magazine, Vol. 19, 179, 1978). However, even when pretreated with these organic carboxylic acid aqueous solutions, sufficient adhesive force could not be obtained for both enamel and dentin. Furthermore, in recent years, a pretreatment material has been devised in which a metal chloride or the like is added to an organic carboxylic acid aqueous solution (JP-A-1-279815). However, the dentin adhesive strength of the adhesive material in which these pretreatment materials and the dental adhesive material are combined is still insufficient, and it has been improved by using the primer coating. However, the complexity of the primer application operation causes problems such as delay of treatment time in clinical practice and insufficient adhesive strength due to poor operation.

[0005]

From the above point of view, the enamel and dentin are pretreated in a batch, and the enamel and dentin are firmly bonded together without requiring a complicated operation such as primer coating. A timber set is desired.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to overcome the above technical problems. As a result, by using a pretreatment material consisting of an organic carboxylic acid aqueous solution under specific conditions, and a dental adhesive composition containing a specific acidic group-containing vinyl monomer and a polymerization initiator, without using a primer, In addition, the inventors have invented a dental adhesive set that can simultaneously treat enamel and dentin and exhibits a strong adhesive force to both.

That is, the present invention provides (A) a pretreatment material comprising an aqueous solution of an organic carboxylic acid or a salt thereof and having a pH of 0.8 to 2.2, and (B) the following general formula (1)

[0008]

[Chemical 2]

(Wherein R ₁ is a hydrogen atom or a methyl group, R 1
₂ is an organic residue having 1 to 20 carbon atoms and 3 to 6 valences which may have an ether bond and / or an ester bond, m is an integer of 2 to 4, and n is an integer of 1 or 2) Dental adhesive comprising an adhesive composition containing 100 parts by weight of a vinyl monomer containing 30% by weight or more of an acidic group-containing vinyl monomer and 0.1 to 3 parts by weight of a polymerization initiator. It is a set of materials.

The pretreatment material of the present invention contains an organic carboxylic acid or its salt and water as main components.

As the organic carboxylic acid, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and their acid anhydrides are used. Examples of monocarboxylic acids and their acid anhydrides are formic acid, acetic acid, lactic acid, pyruvic acid, methacrylic acid, acrylic acid, crotonic acid, (n, iso) valeric acid, benzoic acid, salicylic acid, acetic anhydride, crotonic anhydride. , And benzoic anhydride. Examples of the dicarboxylic acid and its anhydride include tartaric acid, succinic acid, glutaric acid, maleic acid, malonic acid, citraconic acid, (o, m,
p) phthalic acid, succinic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride and the like. Examples of the tricarboxylic acid and its anhydride include citric acid, tricarballylic acid, 1,3,5-pentanetricarboxylic acid, trimellitic acid, and trimellitic anhydride.

The organic carboxylic acid salts include potassium salts, sodium salts, calcium salts of the above-mentioned organic carboxylic acids,
Examples include strontium salt and ammonium salt,
Specifically, 1 sodium citrate, 3 potassium citrate, 3 ammonium citrate, 2 sodium maleate, calcium acetate, ammonium acetate, (n, is
o) There are sodium valerate, sodium benzoate, ammonium benzoate, sodium salicylate and the like.

Among the above organic carboxylic acids, formic acid, acetic acid,
Lactic acid, acrylic acid, crotonic acid, maleic acid, malonic acid, citraconic acid, citric acid, tricarbanilic acid, and 1,3,5-pentanetricarboxylic acid or salts thereof,
It is preferable because it exhibits high adhesive strength to tooth structure. Among them, citraconic acid, lactic acid, 1,3,5-pentanetricarboxylic acid, tricarbanilic acid, acrylic acid or a salt thereof is particularly high in adhesive strength to tooth structure. Is more preferable because

The above organic carboxylic acids or salts thereof may be used alone or in combination of two or more.

In the aqueous solution of the organic carboxylic acid or its salt, the pH is 0.8 to 2.2, preferably 1.0 to 2.0.
It is necessary to adjust the concentration so that it is in between. Even if the adhesive composition of the specific composition of the present invention described below is used, the pH of the adhesive composition is 0.
When it is lower than 8, the adhesive strength to dentin is lowered, and when it is higher than 2.2, the adhesive strength to enamel is lowered. When the pH is in the above range, it exhibits excellent adhesion to both dentin and enamel.

Of these organic carboxylic acids or salts thereof,
Those that are sparingly soluble in water can be dissolved by adding an alcohol such as ethanol to water in an amount of 10 to 50% by weight.
Further, the pretreatment material of the present invention may be blended with a polymer compound such as polyvinylpyrrolidone, carboxymethylcellulose, polyvinyl alcohol or the like, or highly dispersible silica or the like in order to adjust the viscosity, if necessary. Further, an edible dye as a coloring material can be blended. When these optional components are blended, the final pH of the pretreatment material may be adjusted and blended so as to fall within the above range.

The acidic group-containing vinyl monomer used in the adhesive composition of the present invention has a structure represented by the general formula (1). If this specific monomer is not used, excellent adhesive strength to both dentin and enamel will not be exhibited.

In the general formula (1), R ₂ has 3 to 20 carbon atoms and may have an ether bond and / or an ester bond.
~ 6 organic residue and its structure is not particularly limited,
A specific example is as follows.

[0019]

[Chemical 3]

Preferred specific examples of the acidic group-containing vinyl monomer represented by the general formula (1) are as follows.

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Chemical 6]

(However, R ₁ is a hydrogen atom or a methyl group) In addition to the above-mentioned acidic group-containing vinyl monomer, it is also a preferred embodiment to use another vinyl monomer. Typical examples of other vinyl monomers preferably used are those having an acrylic group and / or a methacrylic group, and specific examples are as follows.

A) Monofunctional monomer Methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glyceryl monomethacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates thereof, or acrylic acid,
Methacrylic acid, 2-methacryloyloxyethyl dihydrogen phosphate.

(B) Bifunctional vinyl monomer (i) Aromatic compound type 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2, 2-bis (4
-Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2
(4-methacryloyloxyethoxyphenyl) -2
(4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyl Oxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates thereof (ii) Aliphatic compound system ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and their acrylates c) Trifunctional vinyl monomer trimethylol Propane trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate and their acrylates, and monomers represented by the following structural formulas

[0027]

[Chemical 7]

(However, R ₁ is as defined above) d) Tetrafunctional vinyl monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and urethane type monomer represented by the following structural formula.

[0029]

[Chemical 8]

From the viewpoint of adhesion durability, difunctional or trifunctional vinyl monomers are preferred.

The above vinyl monomers may be used alone or, if necessary, as a mixture of two or more kinds.

The concentration of the acidic group-containing vinyl monomer of the present invention in all vinyl monomers is 30% by weight or more, preferably 50 to 95% by weight. If the addition amount is less than 30% by weight, the adhesiveness of the adhesive composition with the tooth substance is deteriorated.

A filler can be added to the dental adhesive composition of the present invention. This filler is not particularly limited, and inorganic fillers and organic fillers generally used as fillers for dental resin materials may be used alone or in combination.

To give concrete examples of those generally used, as the organic filler, homopolymers or copolymers of acrylic acid ester or methacrylic acid ester,
Polyvinyl chloride, polystyrene, polyester, polyamide and the like. As the inorganic filler, for example, aluminosilicate glass, quartz, amorphous silica, silica-titania, silica-zirconia, silica-alumina, silicate glass, titania, zirconia, alumina, etc. are preferably used. As the inorganic filler, it is usually preferable to use one treated with a silane coupling agent, a titanate coupling agent, a zircoaluminate coupling agent, or the like. The polymerization initiator used in the present invention is not particularly limited,
Known radical generators can be used without any limitation. For example, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane 2,5- Organic peroxides such as dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, etc., azo compounds such as azobisisobutyronitrile, organic acid compounds such as tributyl boric acid, etc. are preferable. is there.

It is also possible to carry out the polymerization at room temperature by using a combination of the above organic peroxide and amine.
As such an amine, a secondary or tertiary amine having an amino group bonded to an aryl group is preferably used in terms of curing acceleration. For example, N, N'-dimethyl-p-toluidine, N, N'-dimethylaniline, N'-β-hydroxyethyl-aniline, N, N'-di (β-hydroxyethyl) -aniline, N, N '. -Di (β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-
Methyl-p-toluidine and the like are preferable.

It is also a preferred embodiment to use a photosensitizer which generates a radical upon irradiation with light, as the polymerization initiator. Examples of the photosensitizer for ultraviolet rays include benzoin, benzoin methyl ether, benzoin ethyl ether, acetoin benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone.
Further, a photosensitizer which initiates polymerization with visible light is more preferably used because it does not require ultraviolet light harmful to the human body. Examples of these are benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,
Examples include α-diketones such as 10-phenanthrenequinone and naphthoquinone. Among them, camphorquinone is most preferably used. It is also preferable to use a combination of the photosensitizer and a photopolymerization accelerator.

Examples of the photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-
Di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N. , N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p
-Dimethylaminobenzoic acid amino ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N
-Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpen, N, N-dimethyl-3,5-xylidine, 4-
Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine,
Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine,
Tertiary amines such as N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol Barbituric acids such as 5-butylbarpituric acid and 1-benzyl-5-phenylbarpituric acid can be preferably used. At least one kind of these photopolymerization accelerators can be selected and used, and two or more kinds can also be mixed and used.

Among these polymerization initiators, a combination of a photosensitizer and a photopolymerization accelerator is preferable in terms of adhesive strength.

The amount of the above-mentioned polymerization initiator added is appropriately determined within the range of 0.1 to 3% by weight based on all vinyl monomers.

The method for mixing the dental adhesive composition of the present invention is not particularly limited, and a usual method is adopted. The packaging form is also not particularly limited, and for example, when the polymerization initiator is a photosensitizer, the vinyl monomer and the polymerization initiator can be packaged in one pack, and, for example, the polymerization initiator is an organic peroxide. In this case, it is possible to divide the vinyl monomer into two, add an organic peroxide to one of them, and add an amine to the other to form a two-pack.

[0041]

The dental adhesive set of the present invention can firmly bond to both enamel and dentin without using a primer.

[0042]

EXAMPLES The dental adhesive set of the present invention will be specifically shown by the following examples, but the present invention is not limited to these examples. The pH of the pretreatment material was measured with a glass electrode type hydrogen ion concentration meter (manufactured by Horiba Ltd.).

Examples 1-9, Comparative Examples 1-2 Camphorquinone was added to a mixture of 80 parts by weight of an acid group-containing vinyl monomer of the following structural formula (2) and 20 parts by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). , P
10 g of dimethylaminobenzoic acid ethyl ester dissolved in 0.5% by weight each and silica 3
3 parts by weight, 11 parts by weight of aluminum hydroxide, 8 parts by weight of artificial cryolite, 21 parts by weight of aluminum phosphate, 7 parts by weight of aluminum fluoride, and 20 parts by weight of calcium fluoride were melted and crushed into a filler. 2% by weight of γ-
Methacryloxypropyltrimethoxysilane (A-17
Adhesive composition A was prepared by mixing 15 g of the powder surface-treated with Nippon Unicar Co., Ltd.) under light shielding and vacuum defoaming to prepare an adhesive composition.

The bovine anterior teeth were removed within 24 hours after the slaughter, and the enamel plane and the dentin plane were carved under water with an # 800 emery paper so as to be parallel to the labial surface. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then they were treated with a pretreatment material having the composition shown in Table 1 for 30 seconds. Then, the pretreated enamel plane and dentin plane are washed with water and dried, and then a double-sided tape with a hole having a diameter of 4 mm is fixed to this plane, and then a hole having a thickness of 1.5 mm and a diameter of 6 mm is opened. Paraffin wax was fixed on the circular hole so as to have the same center, and a simulated cavity was formed.
After filling the adhesive cavity with the adhesive composition A, a visible light irradiator (white light, manufactured by Takara Belmont Co.)
It was irradiated with light for 30 seconds to cure the composition. After the adhesion test piece was immersed in water at 37 ° C. for 24 hours, the adhesion strength with the tooth was measured at a crosshead speed of 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). The results are shown in Table 1.

[0045]

[Chemical 9]

Examples 10 and 11 Camphorquinone, p was added to a mixture of 80 parts by weight of the acidic group-containing vinyl monomer of the above structural formula (2) and 20 parts by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
-Dimethylaminobenzoic acid ethyl ester was dissolved in an amount of 0.5% by weight to prepare a dental adhesive, which was used as an adhesive composition B.

The bovine anterior teeth were removed within 24 hours after the slaughter, and the enamel plane and the dentin plane were carved under water with an # 800 emery paper so as to be parallel to the labial surface. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then they were treated with a pretreatment material having the composition shown in Table 1 for 30 seconds. Then, the pretreated enamel plane and dentin plane are washed with water and dried, and then a double-sided tape with a hole having a diameter of 4 mm is fixed to this plane, and then a hole having a thickness of 1.5 mm and a diameter of 6 mm is opened. Paraffin wax was fixed on the circular hole so as to have the same center, and a simulated cavity was formed.
The adhesive composition B was applied to the bottom surface of this simulated cavity with a small pen, and then irradiated with white light for 10 seconds. Further, a photocurable composite resin (Palfique Esterite, manufactured by Tokuyama Soda Co., Ltd.) was filled therewith, and after pressure contact, light was irradiated for 30 seconds to cure.

After the adhesion test piece was immersed in water at 37 ° C. for 24 hours, the crosshead speed was 1 using an autograph.
The adhesive strength with the tooth was measured at 0 mm / min. The results are shown in Table 1.

Example 12 A mixture of 80 parts by weight of an acid group-containing vinyl monomer represented by the following structural formula (3) and 20 parts by weight of trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added camphorquinone.
10 g of 0.5% by weight of p-dimethylaminobenzoic acid ethyl ester, 33 parts by weight of silica, 11 parts by weight of aluminum hydroxide, 8 parts by weight of artificial cryolite, 21 parts by weight of aluminum phosphate, A powder of 7 parts by weight of aluminum fluoride and 20 parts by weight of calcium fluoride was melted and pulverized to obtain a filler of 2% by weight.
-Methacryloxypropyltrimethoxysilane (A-1
74, manufactured by Nippon Unicar Co., Ltd.), and mixed with 15 g of powder surface-treated with light shielding, and vacuum degassing to prepare an adhesive composition,
This was designated as adhesive composition C.

The adhesive composition C was used to adhere to a tooth in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in Table 1.

[0051]

[Chemical 10]

Example 13 A mixture of 65 parts by weight of an acid group-containing vinyl monomer represented by the following structural formula (4) and 35 parts by weight of hydroxyethyl methacrylate (Kyoeisha Yushi Co., Ltd.) was added camphorquinone and p-dimethylaminobenzoic acid ethyl ester. 15g each of which dissolved 0.5% by weight and quartz powder (VX
S, manufactured by Tatsumori Co., Ltd.) was mixed with 10 g of a powder surface-treated with 2% by weight of γ-methacryloxypropyltrimethoxysilane under light shielding and vacuum defoaming to prepare an adhesive composition. It was designated as Composition D.

The adhesive composition D was used to adhere to a tooth in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in Table 1.

[0054]

[Chemical 11]

Comparative Example 3 A mixture of 20 parts by weight of the acidic group-containing vinyl monomer represented by the structural formula (2) and 80 parts by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to camphorquinone, p.
10 g of dimethylaminobenzoic acid ethyl ester dissolved in 0.5% by weight each and silica 3
3 parts by weight, 11 parts by weight of aluminum hydroxide, 8 parts by weight of artificial cryolite, 21 parts by weight of aluminum phosphate, 7 parts by weight of aluminum fluoride, and 20 parts by weight of calcium fluoride were melted and pulverized into a filler ( Average particle size 1.
(0 μm) was mixed under light shielding and then degassed in vacuum to prepare an adhesive composition, which was used as an adhesive composition E.

The adhesive composition E was used to adhere to a tooth in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in Table 1.

Comparative Example 4 The bovine anterior teeth were removed within 24 hours after slaughter, and under water injection, # 80.
The enamel plane and the dentin plane were carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then they were treated with a pretreatment material having the composition shown in Table 1 for 30 seconds. Then, the pretreated enamel plane and dentin plane were washed with water and dried, and then a double-sided tape having a hole with a diameter of 4 mm was fixed to this plane, and a hole with a thickness of 1.5 mm and a diameter of 6 mm was opened. Paraffin wax was fixed on the circular hole so as to have the same center to form a simulated cavity. The bottom surface of this simulated cavity does not include the acidic group-containing vinyl monomer represented by the general formula (1) of the present invention, but is commercially available with 2-methacryloyloxyethyl phosphate, hydroxymethacrylate and neopentylglycol dimethacrylate as the monomer main components. After applying a clear fill photo bond (manufactured by Kuraray Co., Ltd.) with a small brush, light irradiation was performed for 20 seconds. Further, Palfique Esterite was filled on it, pressed and then irradiated with light for 30 seconds for curing.

After the adhesion test piece was immersed in water at 37 ° C. for 24 hours, the crosshead speed of 1 was measured using an autograph.
The adhesive strength with the tooth was measured at 0 mm / min. The results are shown in Table 1.

Comparative Examples 5 to 6 The bovine anterior teeth were removed within 24 hours after slaughter, and under water injection, # 80.
The enamel plane and the dentin plane were carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then they were treated with a pretreatment material having the composition shown in Table 1 for 30 seconds. Then, the pretreated enamel plane and dentin plane were washed with water and dried, and then a double-sided tape having a hole with a diameter of 4 mm was fixed to this plane, and a hole with a thickness of 1.5 mm and a diameter of 6 mm was opened. Paraffin wax was fixed on the circular hole so as to have the same center to form a simulated cavity.

With respect to dentin, a commercially available clear-fill SA primer (Kuraray Co., Ltd.) containing N-methacryloyl-5-aminosalicylic acid as a main component was applied to the bottom surface with a stylus and dried, and then used in Comparative Example 4. After applying the fill photo bond with a small brush, it was irradiated with light for 20 seconds. Further, Palfique Esterite was filled on it, pressed and then irradiated with light for 30 seconds for curing.

With respect to the enamel, clear fill photo bond was applied to the bottom surface with a small pen, and parfique esterite was filled on the bottom and pressure-contacted, followed by light irradiation for 30 seconds to cure.

After the adhesion test piece was immersed in water at 37 ° C. for 24 hours, the cross head speed was 1 using an autograph.
The adhesive strength with the tooth was measured at 0 mm / min. The results are shown in Table 1.

Comparative Example 7 The bovine anterior teeth were extracted within 24 hours after slaughter, and under water injection, # 80.
The enamel plane and the dentin plane were carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then they were treated with a pretreatment material having the composition shown in Table 1 for 30 seconds. Then, the pretreated enamel plane and dentin plane are washed with water and dried, and then a double-sided tape having a hole with a diameter of 4 mm is fixed to the flat surface, and a paraffin wax having a hole with a diameter of 1.5 mm and a diameter of 6 mm is opened. Were fixed so as to be in the same center on the circular hole to form a simulated cavity. The bottom surface of this simulated cavity does not contain the acidic group-containing vinyl monomer represented by the general formula (1) of the present invention, and 11-methacryloyloxy-
Commercially available adhesive Tokuso Light Bond (manufactured by Tokuyama Soda Co., Ltd.) containing 1,1-undecadicarboxylic acid, hydroxyethyl methacrylate, bisphenol A-diglycidyl methacrylate, and triethylene glycol dimethacrylate as monomer components is applied with a brush. After that, light irradiation was performed for 10 seconds. Further, Palfique Esterite was filled on it, pressed and then irradiated with light for 30 seconds for curing.

After the adhesion test piece was immersed in water at 37 ° C. for 24 hours, the cross head speed of 1 was measured using an autograph.
The adhesive strength with the tooth was measured at 0 mm / min. The results are shown in Table 1.

[0065]

[Table 1]

Claims (1)

[Claims] 1. A pretreatment material comprising (A) an aqueous solution of an organic carboxylic acid or a salt thereof and having a pH of 0.8 to 2.2, and (B) the following general formula: (In the formula, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a carbon atom which may have an ether bond and / or an ester bond.
20 is a trivalent to hexavalent organic residue, m is an integer of 2 to 4, and n is 1.
Or an integer of 2), an adhesive composition containing 100 parts by weight of a vinyl monomer containing 30% by weight or more of an acidic group-containing vinyl monomer and 0.1 to 3 parts by weight of a polymerization initiator. A dental adhesive set characterized in that